JPH10158523A - Cross-link type aqueous emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition that contains a specific polycarbonyl compound and a polyfunctional semicarbazide curing agent and has excellent adhesion of the coating layer to the substrate and resistance to water and solvents. SOLUTION: This composition comprises (A) a polycarbonyl compound and (B) a polyfunctional semicarbazide curing agent and/or a terminal group blocker. The component A contains a carbonyl group-bearing copolymer that is prepared from a monomer mixture containing >=0.5wt.% of an ethylenically unsaturated monomer bearing at least one of aldo group or keto group and has an acid value of >=25mgKOH/g. The component B is derived from a polyisocyanate and is preferably represented by the formula [R<1> is a 2-20 alkylene diisocyanate, a (substituted) 5-20C cycloalkylene diisocyanate; R<2> is a 2-20C alkylene, a 5-20C cycloalkylene; R<3> is H, a 1-20C alkyl; n is 0, 1; 1 and m are each 0 or a positive number, 3<=(1+m)<=20].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinked aqueous emulsion composition useful as a paint, a primer or a finishing material for building materials, an adhesive, a pressure-sensitive adhesive, a paper processing agent and a finishing agent for a woven fabric. In particular, the present invention relates to a crosslinked aqueous emulsion composition obtained by using a specific polycarbonyl compound and a specific semicarbazide-based curing agent.

[0002]

2. Description of the Related Art In recent years, aqueous emulsions have attracted attention in the field of coating as a conversion material from an organic solvent type to an aqueous type. However, they are still insufficient in water resistance, stain resistance, hardness, etc. as compared with organic solvent type coating agents. It does not show proper physical properties. For the purpose of improving these properties, it is common practice to introduce a functional group into an aqueous emulsion to form a crosslinked coating film.

There is a great demand for aqueous emulsions for forming crosslinked coating films to be one-part, room temperature curing from the viewpoint of workability and workability. Recently, hydrazone crosslinking using a dehydration condensation reaction between a carbonyl group and a hydrazine group has been demanded. Aqueous emulsions have attracted attention. For example, Japanese Patent Publication No. 46-20
053, JP-B-58-20991, JP-A-57-3850, JP-A-57-3857,
JP-A-58-96643, WO96 / 01252
In pamphlets and the like, by adding a polyfunctional carboxylic acid hydrazide compound or a semicarbazide derivative having a specific structure as a curing agent to a carbonyl group-containing aqueous emulsion, it has both low-temperature curability and storage stability, and has hardness and stain resistance. Although coating compositions excellent in such properties have been proposed, their adhesion to substrates and water resistance have not been satisfactory. For example, Japanese Patent Application Laid-Open No. 58-10 / 1983
4902, JP-A-62-25163, JP-A-59-8071, JP-A-51-79102, JP-A-62-87534, JP-A-7-261
No. 97, etc., a coating composition using a carboxylic acid dihydrazide compound as a curing agent and introducing a hydrophilic carbonyl group-containing polymer into a carbonyl group-containing aqueous emulsion is proposed. Was not enough.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned drawbacks of a conventional carbonyl group-containing aqueous emulsion composition containing a hydrazine derivative. That is, when a crosslinked coating film is formed, it is an object to provide a crosslinkable aqueous emulsion composition in which the adhesion to a substrate is significantly improved, and further excellent water resistance, durability and initial gloss can be expressed. .

[0005]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above-mentioned problems, and found that the adhesion of the coating film to the substrate, the water resistance, and the water resistance, which could not be expected in the past, were hitherto expected. The present invention, which expresses solvent properties, has been completed. That is, a first aspect of the present invention is a crosslinked aqueous emulsion composition containing a polycarbonyl compound, a polyfunctional semicarbazide-based curing agent and / or a terminal blocker [A] thereof, wherein the polycarbonyl compound is contained in a molecule. The acid value obtained by polymerizing a monomer mixture containing 0.5% by weight or more of an ethylenically unsaturated monomer having at least one ald group or keto group and a carboxylic acid group-containing unsaturated monomer is 25 mg KOH / G or more containing a carbonyl group-containing copolymer [B].

A second aspect of the invention is the crosslinked aqueous emulsion composition according to the first aspect, wherein the polyfunctional semicarbazide-based curing agent is derived from a polyisocyanate compound. A third aspect of the invention is the crosslinked aqueous emulsion composition according to the second aspect of the invention, in which the polyfunctional semicarbazide-based curing agent is represented by the following formula (1).

[0007]

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(Wherein R ¹ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or alkyl group having 1 to 18 carbon atoms,
A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, which is not substituted or has 1 to 1 carbon atoms
C6-20 arylene diisocyanate substituted with an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms A polyisocyanate residue having no terminal isocyanate group, derived from a trimer to a 20-mer oligomer of at least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms substituted with a group, Alternatively, R ¹ represents a triisocyanate residue having no terminal isocyanate group, which is derived from an alkylene diisocyanate having 2 to 20 carbon atoms and substituted with an isocyanatoalkyl group having 1 to 8 carbon atoms. R ² is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 to carbon atoms. Represents an arylene group having 6 to 10 carbon atoms and substituted by an alkoxy group of 8; Each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n is 0 or 1. l and m are each independently 0 or a positive integer, provided that 3 ≦ (l + m) ≦ 20. A fourth aspect of the present invention is that the polycarbonyl compound comprises a carbonyl group-containing copolymer [B] and a polycarbonyl polymer composition [C].
Wherein the polycarbonyl polymer composition [C] contains 0.5% by weight or more of an ethylenically unsaturated monomer having at least one ald group or keto group in a molecule, and other polyunsaturated monomer. The crosslinked aqueous emulsion composition according to the first aspect of the invention, which is an aqueous emulsion composition having an acid value of less than 25 mgKOH / g obtained by polymerizing a monomer mixture containing a saturated monomer.

A fifth aspect of the invention is that the polycarbonyl compound is
The cross-linking type according to the fourth aspect of the present invention, which is an aqueous emulsion composition [D] obtained by polymerizing and forming a carbonyl group-containing copolymer [B] in the presence of a polycarbonyl polymer composition [C] and a monomer mixture. It is an aqueous emulsion composition. A sixth aspect of the present invention provides a polycarbonyl polymer composition (C) in which a polycarbonyl compound is a carbonyl group-containing copolymer (B) at least partially solubilized with an alkali in an aqueous medium and a monomer mixture. The crosslinked aqueous emulsion composition according to the fourth aspect of the invention, which is an aqueous emulsion composition [E] obtained by polymerizing the above.

The aqueous emulsion composition of the present invention can be stored as a single solution, and after application, a crosslinking reaction easily occurs at room temperature as water evaporates from the surface, so that it is easy to handle and the coating film is hydrophilic. Excellent balance of properties and hydrophobicity,
Unprecedented superior performance is obtained. The aqueous emulsion composition of the present invention needs to contain a specific polycarbonyl compound. Specifically, 0.5% by weight or more of an ethylenically unsaturated monomer having at least one ald group or keto group in a molecule is combined with a carboxylic acid-containing unsaturated monomer and other monomers. It is necessary to include a polycarbonyl compound obtained by polymerization.

The ethylenically unsaturated monomer having at least one ald or keto group in the molecule is an ethylenically unsaturated monomer having a carbonyl group containing an ald or keto group. Specifically, acrolein, diacetone acrylamide, diacetone methacrylamide,
Formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, acryloxyalkyl propanals, methacryloxyalkyl propanals, diacetone acrylate, diacetone methacrylate, acetonyl acrylate, 2-hydroxypropyl acrylate acetyl acetate, butane Diol acrylate acetyl acetate and the like can be mentioned.
However, ethylenically unsaturated monomers containing a carbonyl group of carboxylic acids and esters are excluded.

The ald group or keto group participates in the crosslinking reaction as a carbonyl group after the polymerization reaction. The content of the ethylenically unsaturated monomer having an ald group or a keto group in the monomer mixture must be 0.5% by weight or more. Preferably it is 0.5% by weight or more and 20% by weight or less.

When the amount of the ethylenically unsaturated monomer having an ald group or keto group in the monomer mixture is less than 0.5%, the crosslinking point is small and the coating film performance becomes insufficient. In the present invention, it is necessary to impart an acid value to the polymer by copolymerizing an unsaturated monomer having a carboxylic acid group to increase the water solubility. Examples of unsaturated monomers having a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride and itaconic acid, fumaric acid,
And maleic acid half esters.

The other monomer preferably contains an ethylenically unsaturated monomer. Specifically, acrylic ester, methacrylic ester [hereinafter sometimes simply referred to as (meth) acrylic ester. ],
Aromatic monomers such as styrene and vinyltoluene, vinyl esters such as vinyl acetate, vinyl propionate and vinyl persate, vinyl cyanides such as (meth) acrylonitrile, and vinyl halides such as vinyl chloride and vinylidene chloride , Butadiene and the like. Further, various functional monomers such as (meth) acrylamide, vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, N-methylolacrylamide, N-butoxymethylacrylamide, acid phosphooxyethyl methacrylate, and 3-chloromethacrylate -2-acid phosphooxypropyl, methylpropanesulfonic acid acrylamide, divinylbenzene, (poly) oxyethylene mono (meth) acrylate, (poly) propylene glycol (meth) acrylate, allyl (meth) acrylate, (poly) oxyethylene Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, γ- (meth) acryloxypropyl trimethoxy Silane, and the like.

The acrylate or methacrylate includes, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Examples include cyclohexyl acrylate and dodecyl (meth) acrylate. The acid value of the polycarbonyl compound [B] is 25.
mgKOH / g or more. Acid value is 25m
If it is less than gKOH / g, the water solubility of the resulting coating film will be low, so that the adhesion of the coating film to various substrates and the solvent resistance will be insufficient.

Preferably, it is at least 25 mg KOH / g and at least 250
mgKOH / g or less. In the present invention, the carbonyl group-containing copolymer [B] can be obtained by ordinary solution polymerization, but is preferably an aqueous emulsion obtained by subjecting it to emulsion polymerization in an aqueous medium. The aqueous emulsion composition of the present invention needs to contain a polyfunctional semicarbazide-based curing agent and / or a terminal blocker [A] thereof.

The functional group of the curing agent must be a semicarbazide group. By using a semicarbazide group, the hydrophilicity of the coating film can be reduced and good water resistance can be imparted as compared with the case where a conventional hydrazide group is used. The term “polyfunctional” means that the number of NCO functional groups that are semicarbazide groups contained in one molecule of the curing agent is 3 or more and 20 or less.

The polyfunctional semicarbazide-based curing agent of the present invention is obtained from a polyisocyanate compound obtained by oligomerizing a diisocyanate compound and having 3 to 20 NCO groups in one molecule, from the viewpoint of compatibility with the polycarbonyl compound. It is preferable to use those that are derived. A coating film obtained from a crosslinked aqueous composition containing such a semicarbazide curing agent has a high crosslinking ability and can provide a tough film. If the number of NCO groups in one molecule of the polyisocyanate exceeds 20, the number of semicarbazide groups becomes excessive, so that the viscosity of the semicarbazide-based curing agent increases and handling becomes difficult.

In practice, the curing agent of the present invention can be obtained as an aggregate (composition) of molecules having various numbers of functional groups. Therefore, the average number of NCO functional groups of the curing agent as a whole aggregate is as follows:
It is preferably from 2.5 to 20 and more preferably from 3 to 20. When the number of functional groups is less than the above lower limit, good water resistance and the like cannot be obtained due to insufficient crosslinking of the coating film.

Further, the polyfunctional semicarbazide-based curing agent of the present invention is preferably derived from a polyisocyanate compound having a specific structure represented by the following formula (1).

[0021]

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(Wherein R ¹ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms,
A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, which is not substituted or has 1 to 1 carbon atoms
C6-20 arylene diisocyanate substituted with an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms A polyisocyanate residue having no terminal isocyanate group, derived from a trimer to a 20-mer oligomer of at least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms substituted with a group, Alternatively, R ¹ represents a triisocyanate residue having no terminal isocyanate group, which is derived from an alkylene diisocyanate having 2 to 20 carbon atoms and substituted with an isocyanatoalkyl group having 1 to 8 carbon atoms. R ² is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 to carbon atoms. Represents an arylene group having 6 to 10 carbon atoms and substituted by an alkoxy group of 8; Each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n is 0 or 1. l and m are each independently 0 or a positive integer, provided that 3 ≦ (l + m) ≦ 20. The terminal of the semicarbazide group of the curing agent may be blocked from the viewpoint of storage stability, in which case the above formula (1)
At least one of the terminal groups H ₂ NR ³ N— in the above is a blocked body represented by the following formula (2).

R ⁵ R ⁴ C = NR ³ N- (2) (wherein R ⁴ and R ⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, Number 5-2
0 represents a cycloalkyl group or a unsubstituted or substituted with or allyl group having 6 to 10 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms having 1 to 18 carbon atoms,, R ⁴ and R ⁵ may jointly form an annular structure. ).

In the present invention, the semicarbazide-based curing agent (1) represented by the formula (1) is obtained by reacting a polyisocyanate compound having three or more NCO groups in one molecule with a hydrazine derivative. Things. When a compound obtained by reacting a diisocyanate compound having two NCO groups in one molecule with a hydrazine derivative is used as a curing agent, the resulting film has low crosslinking efficiency, and is tough and water resistant. An excellent film cannot be obtained.

In the present invention, the polyisocyanate compound which can be used for producing the semicarbazide-based curing agent represented by the formula (1) has 3 to 20 NCO groups in one molecule.
Polyisocyanate compound having, for example, a diisocyanate buret bond, urea bond, isocyanurate bond, urethane bond, allophanate bond,
Polyisocyanate compounds oligomerized by uretdione bonds and the like, and 1,8-diisocyanato-4-
Isocyanatomethyloctane and combinations thereof.

Among the polyisocyanate compounds, preferred are those having a isocyanurate structure or a burette structure as a basic skeleton in terms of hardness, chemical resistance, heat resistance and the like of a film formed from the coating composition. Can be In addition, examples of those having excellent flexibility of a film obtained from a coating composition with a polycarbonyl compound or the like include those having a urethane structure as a basic skeleton.

Examples of the polyisocyanate compound having an isocyanurate structure as a basic skeleton include an isocyanurate-type polyisocyanate of hexamethylene diisocyanate described in JP-A-55-38380 and JP-A-57-78460. Copolymerized isocyanurate type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate as described in JP-A-57-47321, and isocyanurate modified with a polyfunctional alcohol as described in JP-A-57-47321. Low-viscosity isocyanurate-type polyisocyanate as described in JP-A-64-33115.
A cyclic trimerization reaction of a diisocyanate compound in the presence of a catalyst, such as a highly branched isocyanurate-type polyisocyanate described in US Pat. %, Preferably 10 to 60% by weight, and a polyisocyanate compound having an isocyanurate structure obtained by removing and purifying an excess diisocyanate compound.

Examples of the polyisocyanate compound having a bullet structure as a basic skeleton include, for example, those described in
No. 106797, JP-A-55-11452 and the like, hexamethylene diisocyanate-based bullet type polyisocyanate,
No. 95259, a copolymer of isophorone diisocyanate and hexamethylene diisocyanate represented by a burette-type polyisocyanate and the like. Agent / diisocyanate in an equivalent ratio of 1/2 to 1/100, preferably 1
After reacting at / 3 to 1/50, a polyisocyanate compound having a buret structure obtained by removing and purifying an excess diisocyanate compound is exemplified.

As a polyisocyanate compound having a urethane structure as a basic skeleton, for example, JP-A-61-2
No. 8518 and JP-A-4-50277, etc., after reacting polycaprolactone polyol and diisocyanate at an equivalent ratio of -NCO / -OH of 5 to 40, and removing and purifying excess diisocyanate. The resulting urethane-type polyisocyanate is exemplified. In particular, when the molecular weight is less than 2,000, in addition to flexibility, water resistance, heat resistance and the like are excellent, and high hardness can be exhibited.

The polyisocyanate compound having 3 to 20 NCO groups in one molecule can be obtained by using the following diisocyanate compound. As such a diisocyanate compound, a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms,
A cycloalkylene diisocyanate having 5 to 20 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, An arylene diisocyanate having 6 to 20 carbon atoms which is not substituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or alkyl group having 1 to 18 carbon atoms or It is at least one diisocyanate compound selected from the group consisting of aralkylene diisocyanates having 8 to 20 carbon atoms and substituted with an alkoxy group having 1 to 8 carbon atoms.

Examples of the diisocyanate compound include alkylene diisocyanates such as hexamethylene diisocyanate (HDI); 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), and dimethylcyclohexane diisocyanate (hydrogenated XDI). 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof (TDI), diphenylmethane-4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI) ), 3,3-dimethyl-4,4-
Biphenylene diisocyanate (TODI), crude TD
I, polymethylene polyphenyl diisocyanate, crude MDI, arylene diisocyanate such as phenylene diisocyanate, xylylene diisocyanate (XD
Aralkylenediisocyanates such as I) and the like, and combinations thereof.

Among these diisocyanate compounds, alkylene diisocyanate and cycloalkylene diisocyanate are preferable from the viewpoints of heat yellowing resistance and weather resistance of a film using the formed semicarbazide compound. The polyisocyanate compound is reacted with hydrazine or a derivative thereof to obtain a polyfunctional semicarbazide-based curing agent.

The hydrazine derivatives used in the present invention include, for example, hydrazine and hydrates thereof; monoalkyl-substituted hydrazine compounds such as monomethylhydrazine, monoethylhydrazine and monobutylhydrazine;
Dihydrazine compounds such as 1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine; oxalic acid dihydrazide, malonic acid dihydrazide;
Tricarboxylic acid dihydrazide such as tricarboxylic acid dihydrazide such as succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, isophthalic acid dihydrazide, phthalic acid dihydrazide and the like; Examples include trihydrazides, carbonic dihydrazides represented by the general formula (3), bissemicarbazides represented by the general formula (4), and the like, and combinations thereof.

[0034]

Embedded image

(In the formula, x represents an integer of 0 or 1.)

[0036]

Embedded image

(Wherein R ⁸ is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, unsubstituted or 1
Represents an arylene group having 6 to 10 carbon atoms and substituted by an alkyl group having 18 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. In the production of the semicarbazide-based curing agent of the present invention, an NCO group of a polyisocyanate compound having three or more NCO groups in one molecule and a terminal group represented by the following formula (5) in a hydrazine derivative and a terminal group derived therefrom The equivalent ratio to the total number of blocked end groups is 1: 1.5 to 1: 100, preferably 2: 5 to 5.
1:50.

—NR ¹¹ NH ₂ (5) (In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) After the completion of the reaction, the excess hydrazine derivative is optionally distilled, It can be removed by extraction or the like. In the present invention, hydrazine or a derivative thereof is represented by the following formula (6) for the purpose of preventing a semicarbazide-based curing agent or a polyisocyanate compound as a raw material thereof from being polymerized by chain extension of hydrazine or a derivative thereof. Hydrazones, and react with monoaldehydes or monoketones.

R ⁹ R ¹⁰ C ＝ O (6) (wherein, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, 5 carbon atoms
To 20 cycloalkyl groups, or unsubstituted or C1 to C18 alkyl groups or C1 to C8
It represents an aryl group having 6 to 10 carbon atoms substituted with an alkoxyl group, R ^9, R ¹⁰ may form a cyclic structure jointly in some cases. In this case, the resulting semicarbazide-based curing agent is a semicarbazide group in which the semicarbazide group is blocked as a semicarbazone group. Elimination of the monoaldehyde or monoketone used as a blocking agent from the semicarbazide-based curing agent may be hydrolyzed and distilled off before mixing with the polycarbonyl compound,
The composition may be used as it is as a curing agent to form a crosslinked aqueous composition, applied to the surface of a substrate, and then spontaneously released during the curing process. Therefore, a monoketone having a boiling point of 30 to 200 ° C. (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) is preferred as the blocking agent.

The polycarbonyl compound of the present invention may contain at least the carbonyl group-containing polymer [B], but preferably further contains a polycarbonyl polymer composition [C]. Polycarbonyl polymer composition [C]
Is 0.5 to 20% by weight of an ethylenically unsaturated monomer having at least one ald group or keto group in the molecule,
It is obtained by polymerizing a monomer mixture containing other unsaturated monomers.

The acid value of the polycarbonyl polymer composition [C] is different from that of the carbonyl group-containing polymer [B] by 25 mg.
It is necessary to be less than KOH / g, preferably 1-2.
2 mgKOH / g. Outside this range, sufficient water resistance of the coating film cannot be obtained. The acid value of the polycarbonyl compound [B] needs to be 25 mgKOH / g or more. When the acid value is less than 25 mgKOH / g, the water solubility of the obtained coating film is low, and thus the adhesion of the coating film to various substrates and the solvent resistance become insufficient.

At this time, the carbonyl group-containing copolymer [B]
The solid content weight ratio to the polycarbonyl polymer composition [C] is preferably 0.001 to 2.0,
More preferably, it is 0.01 to 0.5. In the present invention, a method for obtaining a polycarbonyl compound containing both the carbonyl group-containing copolymer [B] and the polycarbonyl polymer composition [C] is not particularly limited, but preferred examples include the following methods. it can.

A method for obtaining a polycarbonyl compound by separately polymerizing the polycarbonyl polymer composition [C] and the carbonyl group-containing polymer [B] and then mixing them. In this case, the polycarbonyl compound is a simple mixture of [B] and [C]. A method of obtaining an aqueous emulsion composition [D] by polymerizing and forming a carbonyl group-containing copolymer [B] in the presence of a polycarbonyl polymer composition [C] and a monomer mixture. In this case, the aqueous emulsion composition [D] has each emulsion of the polycarbonyl polymer composition [C] as a central core,
It is presumed that the carbonyl group-containing copolymer [B] is mainly composed of a multi-layered emulsion formed by polymerization. The carbonyl group-containing copolymer [B]
Is preferably formed by emulsion polymerization.

In an aqueous medium, a polycarbonyl polymer composition [C] is formed by emulsion polymerization in the presence of a monomer mixture with a carbonyl group-containing copolymer [B] at least partially solubilized by an alkali. A method for obtaining an aqueous emulsion composition [E]. In this case, if the embodiment is shown as a specific production method, the carbonyl group-containing copolymer [B] may be subjected to water dispersion or solubilization treatment in an aqueous medium after solution polymerization, or emulsion polymerization in an aqueous medium. Or a solubilization treatment after emulsion polymerization to obtain an aqueous dispersion or aqueous solution of the carbonyl group-containing copolymer [B], and an aqueous dispersion or aqueous solution of the carbonyl group-containing copolymer [B] in an aqueous medium. It is obtained by forming a polycarbonyl polymer composition [C] by emulsion polymerization in the presence of an aqueous solution and a suitable monomer mixture.

In this case, it is considered that the solubilized carbonyl group-containing copolymer [B] functions as a kind of surfactant and has an action of emulsifying and dispersing the polymer of the polycarbonyl polymer composition [C]. In the present invention, the aqueous dispersion of the carbonyl group-containing copolymer [B], the polycarbonyl polymer composition [C], the aqueous emulsion composition [D], and the aqueous emulsion composition [E] are each prepared by mixing a monomer mixture with an aqueous medium. In the case where it is obtained by subjecting it to emulsion polymerization in the inside, as a method for adjusting the emulsion polymerization, emulsion polymerization can be carried out using a usual emulsifier.

In the present invention, ordinary surfactants such as fatty acid soaps, alkyl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl aryl sulfates, p- Nonionic surfactants such as anionic surfactants such as styrene sulfonates and polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan fatty acid esters, and oxyethylene oxypropylene block copolymers are used. In order to improve the water resistance of the film obtained from the product, at least one of the surfactants is an anionic reactive surfactant, that is, an ethylenically unsaturated monomer having a sulfonic acid group or a sulfonate group, and a carbonyl group-containing monomer. Copolymer dispersion, polycal Sulfonyl polymer composition (C), the aqueous emulsion composition (D) or an aqueous emulsion composition (E)
It is preferable to use 0.05 to 20% by weight as a solid content weight ratio to the above. Specifically, for example, Sanyo Chemical Co., Ltd.
Eleminol (trademark) JS-2 and JS-5 manufactured by Kao Corporation, and Latemul (trademark) S-120 and S-180 manufactured by Kao Corporation.
A, S-180, Aqualon (trademark) HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adecaria Soap (trademark) SE-1025N manufactured by Asahi Denka Kogyo KK, salt of sulfoalkyl methacrylate, p- There are salts of styrene sulfonic acid and the like, used alone or in combination of two or more, or used in combination with a usual surfactant or a nonionic reactive surfactant.

In the present invention, the carbonyl group-containing copolymer [B], the polycarbonyl polymer composition [C], the aqueous emulsion composition [D] or the aqueous emulsion composition [E] may be used in an aqueous medium, if desired. A part may be solubilized by the addition of an alkali and / or an organic solvent. Examples of the alkali used for each solubilization treatment include sodium hydroxide, potassium hydroxide, sodium bicarbonate, organic amines, ammonia, and the like, and the addition thereof is performed before, during, or after the polymerization. May be. The organic solvent used for the solubilization treatment may be supplementarily used when the water-solubilization is insufficient only by the addition of an alkali, or may be solubilized only by the organic solvent.
The organic solvent used is not particularly limited, but specifically, texanol, ethylene glycol monobutyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Examples thereof include mono 2-ethylhexyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, benzyl alcohol, dimethyl glutarate, and isopropyl glutarate.

In the present invention, the carbonyl group-containing copolymer [B], the polycarbonyl polymer composition [C], the aqueous emulsion composition [D], and the aqueous emulsion composition [E]
It is also possible to add a chain transfer agent during the polymerization process for the purpose of adjusting the molecular weight in order to facilitate the solubilization treatment of. Specific examples include mercaptans such as butyl mercaptan and dodecyl mercaptan, alcohols such as methanol and isopropyl alcohol, and α-methylstyrene dimer.

The radical polymerization catalyst used in the present invention is one capable of radically decomposing by heat or a reducing substance to cause addition polymerization of an ethylenically unsaturated monomer. Oxides and azobis compounds can be used. Examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane)
Hydrochloride, 2,2-azobis (2,4-dimethylpareronitrile) and the like are preferable, and in the case of emulsion polymerization, a water-soluble one is preferably used, and the amount thereof is at least one ald group or at least one in the molecule. It is usually added in an amount of 0.1 to 1% by weight based on the total amount of the ethylenically unsaturated carbonyl group-containing monomer having a keto group and other monomers. When it is desired to accelerate the polymerization rate and further perform polymerization at a low temperature, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or Rongalite is used in combination with a radical polymerization catalyst.

The reaction for obtaining the semicarbazide-based curing agent of the present invention can be carried out either in the presence or absence of a solvent. Solvents which are inert to the NCO groups or less active than the reaction components can be used. Specifically, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone cyclohexanone; ether solvents such as dioxane, tetrahydrofuran and diethylene glycol dimethyl ether; amide solvents such as dimethylformamide and dimethylacetamide; N-methyl-2-pyrrolidone; Lactam solvents, sulfoxide solvents such as dimethyl sulfoxide, ethyl acetate, ester solvents such as cellosolve acetate,
alcohols such as t-butanol and diacetone alcohol, aromatic hydrocarbon solvents such as toluene and xylene, n
And aliphatic hydrocarbon solvents such as hexane and the like, and combinations thereof.

Further, the semicarbazide-based curing agent represented by formula (1) and / or the semicarbazide-based curing agent in which the semicarbazide group is blocked as a semicarbazone group assists dispersion stability and solubility in an aqueous medium. For this purpose, a hydrophilic group-containing compound represented by the following formula (7) and at least one selected from the group consisting of a compound in which a semicarbazide group is blocked as a semicarbazone group can be used as a mixture.

[0052]

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(Wherein R ¹² represents a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms,
A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, which is not substituted or has 1 to 1 carbon atoms
Arylene diisocyanate having 6 to 20 carbon atoms substituted with an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or an alkyl group having 1 to 18 carbon atoms or having 1 to 8 carbon atoms Polyisocyanate residue having no terminal isocyanate group derived from at least one trimer to 20-mer oligomer of diisocyanate selected from the group consisting of aralkylene diisocyanates having 8 to 20 carbon atoms substituted with an alkoxy group or R ¹² represents a triisocyanate residue without derived from alkylene diisocyanates having 2 to 20 carbon atoms which is substituted with isocyanatoalkyl group having 1 to 8 carbon atoms, terminal isocyanate groups; R ¹³ is A linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms Or unsubstituted or substituted or represents an arylene group having 6 to 10 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms having 1 to 18 carbon atoms; each R ¹⁴ is independently Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; n is 0 or 1, p and q are each 0 or a positive integer, r is a positive integer, 0 ≦ (p + q) and 2 ≦ (p + q + r)
≦ 20. The compound in which the semicarbazide group of the semicarbazide-based curing agent represented by the formula (7) is blocked as a semicarbazone group has at least one of the terminal groups H ₂ NR ¹⁴ N— in the formula (7) represented by the formula R ⁵ R ⁴ Having a blocked terminal group represented by C ＝ NR ¹⁴ N— (wherein R ⁴ and R ⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms) A cycloalkyl group having 5 to 20 carbon atoms, or an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms or an allyl group having 6 to 10 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms. , R ⁴ and R ⁵ may optionally form a cyclic structure together.)

That is, at least one selected from the semicarbazide curing agent represented by the formula (1) and the terminal blocker thereof, and at least one selected from the hydrophilic group-containing compound represented by the formula (7) and the terminal blocker thereof And curing of the composition containing one of them with an aqueous dispersion of a carbonyl group-containing copolymer [B], a polycarbonyl polymer composition [C], an aqueous emulsion composition [D], or an aqueous emulsion composition [E]. It can be used advantageously as an agent.

As described above, the semicarbazide curing agent of the present invention and the terminal blocker thereof include an aqueous dispersion of the carbonyl group-containing copolymer [B], a polycarbonyl polymer composition [C], and an aqueous emulsion composition [ D] or at least one state selected from the group consisting of dispersion in an aqueous medium and dissolution in an aqueous medium so as to be easily mixed with the aqueous emulsion composition [E].

In some cases, the semicarbazide curing agent and the terminal-blocked body thereof of the present invention may contain a compound other than the hydrophilic group-containing compound represented by the above formula (7) and the compound in which the semicarbazide group is blocked as a semicarbazone group. And other surfactants may be added. Examples of such surfactants include anionic surfactants such as fatty acid soap, alkyl sulfonic acid, alkyl succinic acid, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl allyl sulfate, and polyoxyethylene alkyl allyl ether. ,
Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, oxyethylene oxypropylene block copolymers, known reaction products of ethylene oxide and phosphoric acids, and cationic surfactants containing quaternary ammonium salts and the like; Saponification) Polymer dispersion stabilizers such as polyvinyl alcohol and the like, and combinations thereof.

However, as the surfactant, a hydrophilic group-containing compound represented by the formula (7) and a compound in which a semicarbazide group is blocked as a semicarbazone group have an affinity with a semicarbazide curing agent and a terminal-blocked body thereof. Is particularly preferred because the In particular, at least one selected from the semicarbazide curing agent represented by the formula (1) and the terminal blocker thereof, and at least one selected from the hydrophilic group-containing compound represented by the formula (7) and the terminal blocker thereof Which comprises at least one selected from a semicarbazide curing agent represented by the formula (1) and a terminal blocker thereof, and a hydrophilic group-containing compound represented by the formula (7) and a terminal blocker thereof A weight ratio to at least one selected from the group consisting of = 99/1 to 10/90, an aqueous dispersion of a carbonyl group-containing copolymer [B], a polycarbonyl polymer composition [C], Aqueous emulsion composition [D],
When used as a curing agent for each of the aqueous emulsion compositions [E], a crosslinked aqueous composition that is particularly stable and has excellent curing performance can be obtained.

At least one member selected from the semicarbazide curing agent represented by the formula (1) of the present invention and a terminal-blocked body thereof.
As a specific method for obtaining a composition containing a compound having a hydrophilic group represented by the formula (7) and at least one selected from the terminal blockers thereof, the following two methods are exemplified. Can be. [I] a polyisocyanate compound having three or more NCO groups in one molecule and an active hydrogen compound having a nonionic hydrophilic group and / or an ionic (including those which can be converted into an ionic) hydrophilic group; Is reacted in excess of NCO groups and then reacted with a hydrazine derivative. [Ii] A method of separately synthesizing and mixing the semicarbazide-based curing agent (1) and the hydrophilic group-containing compound represented by the formula (7).

The above two methods can be used in combination, or another method may be used. First, the method (i) will be specifically described.
Examples of the polyisocyanate compound having three or more CO groups include those exemplified as the raw materials used for producing the above-described semicarbazide-based curing agent (1).

In addition, of the active hydrogen compounds having a nonionic hydrophilic group and / or an ionic (including those which can be converted into an ionic) hydrophilic group used in the method (i), the nonionic hydrophilic compound may be used. Examples of the group include polyether polyols such as polyethylene glycol, polyoxyethyleneoxypropylene (random and / or block) glycol, and polyoxyethylene-oxytetramethylene (random and / or block) glycol. Examples include polyethylene glycol monoalkyl ethers represented by the following general formula (8).

[0061]

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(Wherein, R ¹⁵ represents an alkyl group having 1 to 25 carbon atoms, and n represents an integer of 5 to 80). Examples of the ionic hydrophilic group include tertiary amine salts of carboxylic acids and the like. Examples include an anionic group and a cationic group such as a quaternary ammonium salt. Examples of the active hydrogen compound having an anionic group (or a group which can be converted into an anionic group later) include, for example, α,
α, α′-Dimethylolalkanoic acids such as α′-dimethylolpropionic acid and α, α′-dimethylolacetic acid, and the like, preferably lactic acid, glycolic acid,
Monohydroxycarboxylic acids such as hydroxybutyric acid and P-phenolcarboxylic acid; amino acids such as glycine, alanine, aspartic acid and β-alanine; monohydroxysulfonic acids such as P-phenolsulfonic acid; aminosulfonic acids such as taurine; , And combinations thereof. The acid group of these active hydrogen compounds can be converted to an anionic group by neutralizing with a base at the time of synthesis of a hydrophilic polyisocyanate reactant, or emulsification or solubilization in an aqueous medium, but is preferably a hydrophilic polyisocyanate. Used during synthesis of reactants. Specific examples of the base include amine compounds such as triethylamine, ammonia, diethanolamine, dimethylaminoethanol, methyldiethanolamine, and dibutylamine; KOH, Na
Examples thereof include hydroxides of alkali metals such as OH and LiOH, and combinations thereof.

Examples of the active hydrogen compound having a cationic group (or a group that can be converted into a cationic group later) include N-alkyldialkanolamines such as N-methyldiethanolamine and N-butyldiethanolamine, and the number of carbon atoms thereof. Examples thereof include adducts of 2 to 4 alkylene oxides (e.g., ethylene oxide and propylene oxide), preferably N, N-dialkylmonoalkanolamines such as N, N-dimethylethanolamine and N, N-diethylethanolamine. And the combination of these. The tertiary amino group of these active hydrogen compounds is converted to a cationic group by neutralizing with an acid or quaternizing with an alkylating agent during the synthesis of a hydrophilic polyisocyanate compound or during emulsification or solubilization in an aqueous medium. it can. As the acid used for neutralization, for example, acetic acid,
Lactic acid, hydrochloric acid, phosphoric acid, sulfuric acid, and the like, and combinations thereof. Examples of the alkylating agent include dimethyl sulfate, diethyl sulfate, methyl chloride, methyl iodide, benzyl chloride and the like.

A polyisocyanate compound having three or more NCO groups in one molecule and an active hydrogen compound having a nonionic hydrophilic group and / or an ionic (including a compound which can be later converted to an ionic) hydrophilic group The reaction is carried out at a temperature of about 20 ° C. to about 130 ° C. under substantially anhydrous conditions with NCO
Ratio of active groups capable of reacting with NCO groups to NCO groups 1.1
/ 1 to 500/1, preferably 2/1 to 100/1.

These reactions can be carried out without a solvent or in a solvent, if necessary, using a catalyst. As the above-mentioned solvent, those which are inert to the NCO group or have lower activity than the reaction components can be used. Specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as dioxane, tetrahydrofuran and diethylene glycol dimethyl ether; amide solvents such as dimethylformamide and dimethylacetamide; N-methyl-2-pyrrolidone Lactam solvents such as dimethyl sulfoxide; ester solvents such as ethyl acetate and cellosolve acetate; t-butanol;
Alcohols such as diacetone alcohol; aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as n-hexane and the like, and combinations thereof.

Specific examples of the above-mentioned catalyst include salts of metals such as dibutyltin dilaurate, stannous octylate, lead octylate and organic and inorganic acids, and organic metal derivatives; and organic metal derivatives such as triethylamine and triethylenediamine. Secondary amines; and diazabicycloundecene-based catalysts. In the method [i], the thus obtained 1
A reaction product of a polyisocyanate compound having three or more NCO groups in a molecule and an active hydrogen compound having a nonionic hydrophilic group and / or an ionic (including those which can be later converted to an ionic) hydrophilic group At least one selected from the semicarbazide curing agent represented by the formula (1) of the present invention and its terminal blocker by reacting the hydrazine derivative according to the reaction conditions in the production of the semicarbazide curing agent (1); A composition containing a hydrophilic group-containing compound represented by the formula (7) and at least one selected from terminal-blocking bodies thereof is obtained.

Next, the method [ii] will be specifically described. The compound containing a hydrophilic group represented by the formula (7) and the terminal blocker thereof are polyisocyanates having two or more NCO groups in one molecule. By reacting the compound with an active hydrogen compound having a nonionic hydrophilic group and / or an ionic (including a compound which can be later converted to an ionic) hydrophilic group and, if necessary, the above-mentioned hydrazine derivative can get.

The polyisocyanate compound having two or more NCO groups in one molecule includes the polyisocyanate compound having three or more NCO groups in one molecule used in the production of the semicarbazide-based curing agent (1) and its raw material. Examples include the diisocyanate compounds described above. In the synthesis of the hydrophilic group-containing compound represented by the formula (7) and its terminal blocker, a polyisocyanate compound having two or more NCO groups in one molecule and a nonionic hydrophilic group and / or an ionic compound The reaction with an active hydrogen compound having a hydrophilic group (including those which can be converted to an ionic system) is performed by NC
The equivalent ratio of the O group to the active hydrogen group capable of reacting with the NCO group is 1 to
Perform at 10: 1. Other reaction conditions follow the method of [i]. In the crosslinked aqueous composition of the present invention, the ratio of the solid content of the polycarbonyl compound to the polyfunctional semicarbazide curing agent and its terminal blocker [A] is 99.
It is preferably from 1 / 0.1 to 10/90.

In the crosslinked aqueous composition of the present invention, the pH is preferably adjusted to 3 to 10 in order to maintain the long-term dispersion stability of the aqueous dispersion simultaneously with or separately from the solubilization treatment, and the pH is adjusted to 6 to 9 It is more preferable to adjust the range. In the composition of the present invention, components usually added and blended into a water-based paint or the like, for example, a thickener, an antifoaming agent, a pigment, a dispersant, a dye,
The addition of a preservative or the like is optional.

The coating film obtained from the composition of the present invention is useful as a paint, an undercoating or finishing material for building materials, an adhesive, a pressure-sensitive adhesive, a paper processing agent, and a finishing agent for a woven fabric. Concretely, as a base material or a finishing material for building materials, concrete, cement mortar, slate board, scallop board, gypsum board, extruded board, inorganic building materials such as foamable concrete, building materials based on woven or nonwoven fabric It is useful as a paint or an architectural finish for various bases such as metal building materials, as a multi-layer finish paint, a synthetic resin emulsion paint such as gloss paint, a metal paint, a plastic paint, a wood paint, and a tile paint. Examples of the adhesive include a wet adhesive and a contact adhesive for metal, plastic, wood, slate, paper, cloth, and the like used as an adhesive for automobile interiors, an adhesive for building members, a laminate adhesive for various films, and the like. No. Examples of the pressure-sensitive adhesive include a permanent pressure-sensitive adhesive and a re-peelable pressure-sensitive adhesive used for single-sided tape, double-sided tape, label, album and the like.

[0071]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference examples, examples and comparative examples. The parts and percentages in the examples are by weight. The measuring methods of various measurements used in the examples are as follows. Molecular weight distribution: It was determined from a calibration curve of a polystyrene standard using gel permeation chromatography.

(Equipment used) ・ Liquid chromatograph: HLC-8020 manufactured by Tosoh Corporation ・ Column: TSKgel G-5000 HXL TSKgel G-4000 HXL TSKgel G-2000 HXL ・ Data processing apparatus: Tosoh ( Co., Ltd. SC8010 Carrier: Tetrahydrofuran Infrared absorption spectrum is JASCO FT / IR
It was measured by -5300 (manufactured by JASCO Corporation). The solvent resistance of the film was determined using a mixture of the emulsion and the curing agent of each Example or Comparative Example and a film-forming aid in accordance with Formulation A, and then using the applicator to prepare the mixture.
It was applied on a glass plate to a thickness of 5 mm, formed into a film at room temperature, and then dried at room temperature for one month to obtain a transparent and smooth film. The film was placed in a 200-mesh wire mesh bag, immersed in toluene at room temperature for 24 hours, and the retention of the film weight was determined by (film weight after immersion in toluene).
(Film weight before immersion in toluene) × 100. (Formulation A) Mixture of the emulsions of Examples and Comparative Examples with a curing agent (solid content conversion) 460.0 parts Ethylene glycol monobutyl ether 60.0 parts Ethylene glycol mono 2-ethylhexyl ether 10.0 parts Water 30.0 parts The water resistance of the film was determined by mixing a film-forming aid according to Formulation A with respect to the mixture with the emulsion curing agent of each Example or Comparative Example, and then using the applicator to mix the mixture with a 0.10 m
After coating on a glass plate to a thickness of m and forming a film at room temperature, it was further dried at room temperature for one month to obtain a transparent and smooth film. The film as formed on the glass plate was immersed in water at 50 ° C. for 8 hours, and the state of the film was visually observed.

<Judgment Criteria> A: No whitening is observed. ；: Slightly bluish whitening is observed. Δ: slight whitening is observed. ×: Whitening was observed on the entire surface, and some blisters occurred. PP Board Adhesion (PP Adhesion) A mixture of the emulsion and the curing agent of each Example or Comparative Example was blended with a film-forming aid according to Formulation A, and this mixture was dried using a wire coater to a dry film thickness of 0.25 mm. Is applied on a polypropylene plate (abbreviated as PP plate) to a thickness of. After film formation at room temperature, it is further dried at room temperature for one month,
A transparent and smooth film was obtained. The test piece was subjected to a peel test using an adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.), and the peel state was observed.

[0074] Initial Gloss Value, Gloss Retention For the mixture of the emulsion and the curing agent of each Example or Comparative Example, the paint obtained by the following formulation B was coated with a wire coater No. Using 50, apply to a sulfated alumite plate and dry at room temperature for 30 days. The 60 ° 60 ° specular reflectance at that time was measured as an initial gloss value (this is defined as zero time). Subsequently, an exposure test (rain cycle: 12 minutes / hour, black panel temperature: 60 to 66 ° C.) was performed using a sunshine type weatherometer (manufactured by Suga Test Instruments Co., Ltd., product name: WELSUNDC). Exposure 150
Measure the gloss value of the 60 ° 60 ° specular reflectance after 0 hour,
The gloss retention was calculated by dividing by the initial gloss value. (Blend B) Pigment dispersion 82.5 parts Poise 530 * 1 7.5 parts 5% aqueous solution of sodium tripolyphosphate 7.5 parts 3% aqueous solution of Daicel HEC SP-600 * 2 25.0 parts Nopco 1497VD * 3 2.5 parts Taipaque CR-97 Note 4 375.0 parts Let down Mixture of emulsion and curing agent of Examples and Comparative Examples (solid content) 460.0 parts Ethylene glycol monobutyl ether 60.0 parts Ethylene glycol mono 2 -Ethylhexyl ether 10.0 parts Water 30.0 parts Nopco 1497VD 1.0 parts (Note) Note 1 Dispersant: Kao Corporation Note 2 Thickener: Daicel Chemical Industries Ltd. Note 3 Antifoaming agent: * 4 Rutile type titanium oxide: manufactured by Ishihara Sangyo Co., Ltd. Water resistance of coated film Ta No. Using No. 50, it was applied to a sulfated alumite plate and dried at room temperature for 2 hours. After further drying at 50 ° C. for 2 days, it was immersed in water at 40 ° C. for 30 days, and the state was visually determined.

<Judgment Criteria> A: No blistering or shine is observed. ○: Some blisters, but no gloss. Δ: Blisters and gloss are observed. ×: The entire surface is blistered and gloss is remarkable.

[0076]

REFERENCE EXAMPLE 1 With respect to the preparation of an aqueous dispersion of a carbonyl group-containing copolymer, an emulsion (1) was synthesized. In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 8 parts of methacrylic acid, 3 parts of diacetone acrylamide, 44 parts of methyl methacrylate, 45 parts of butyl acrylate, 300 parts of water, 300 parts of diester ammonium sulfosuccinate 20 parts of a 20% aqueous solution of a salt (product name: Latemul S-180A, having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule, manufactured by Kao Corporation) is charged, and a reaction vessel is charged. The temperature inside is raised to 78 ° C. and then 0.5 part of ammonium persulphate is added and kept for 1 hour. Thus, a seed latex in the first stage was prepared, and the hydrogen ion concentration was measured to be PH 1.8. Next, a mixed solution of 32 parts of methacrylic acid, 12 parts of diacetone acrylamide, 176 parts of methyl methacrylate, and 180 parts of butyl acrylate, 330 parts of water, 20 parts of a 20% aqueous solution of latemul S-180A, and 1.0 part of ammonium persulfate Parts of the mixed solution are allowed to flow into the reaction vessel from separate dripping tanks over 3 hours.
During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours.
After cooling to room temperature, the hydrogen ion concentration was measured.
It was 8. After adding 500 parts of water, the pH was adjusted to pH 8 by adding a 25% aqueous ammonia solution, and the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.02% of the total monomer. The solid content of the obtained emulsion was 30.0%.

[0077]

REFERENCE EXAMPLE 2 Emulsion (2) was synthesized for preparing a carbonyl group-containing emulsion composition. In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 230 parts of water and 20% of latemul S-180A were added.
5 parts of an aqueous solution is charged, and the inside of the reaction vessel is heated to 80 ° C. Next, 10 parts of methacrylic acid, diacetone acrylamide 1
5 parts, a mixture of 250 parts of methyl methacrylate and 225 parts of butyl acrylate, 400 parts of water, and Latemul S-180
A mixture of 20 parts of a 20% aqueous solution of A and 1.5 parts of ammonium persulfate is allowed to flow into the reaction vessel from separate dropping tanks over 4 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.1. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.15% of the total monomer. The solid content of the obtained emulsion was 43.0%, and the average particle size was 1180 °.
Met.

[0078]

Reference Example 3 With respect to the preparation of an aqueous emulsion composition, an emulsion (3) was synthesized. 230 parts of water and 5 parts of a 20% aqueous solution of Latemul S-180A are charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, and the inside of the reaction vessel is heated to 80 ° C. Next, a mixture of 8 parts of methacrylic acid, 12 parts of diacetone acrylamide, 200 parts of methyl methacrylate, and 180 parts of butyl acrylate, 300 parts of water, 16 parts of a 20% aqueous solution of latemul S-180A, and 1.2 parts of ammonium persulfate Parts of the mixed solution are allowed to flow into the reaction vessel from separate dripping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow, the temperature in the reaction vessel is maintained at 80 ° C. Subsequently, methacrylic acid 8
Parts, a mixture of 3 parts of diacetone acrylamide, 44 parts of methyl methacrylate, and 45 parts of butyl acrylate, and 10 parts of water
0 parts, a mixed solution of 4 parts of a 20% aqueous solution of latemul S-180A and 0.3 parts of ammonium persulfate are allowed to flow into the reaction vessel from separate dropping tanks over 1 hour. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured to be 1.8.
After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.15% of the total monomer. The solid content of the obtained emulsion is 43.0.
%, Average particle diameter 1240 °.

[0079]

Reference Example 4 With respect to preparation of an aqueous composition, an emulsion (4) was synthesized. In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 8 parts of methacrylic acid, 3 parts of diacetone acrylamide, 44 parts of methyl methacrylate, 45 parts of butyl acrylate, 300 parts of water, and Latemul S-180A 20 parts of a 20% aqueous solution is added, the temperature in the reaction vessel is increased to 78 ° C., and 0.5 parts of ammonium persulfate is added and maintained for 1 hour. A 25% aqueous ammonia solution is added to PH7. Next, methacrylic acid 3
A mixture of 12 parts, 12 parts of diacetone acrylamide, 205 parts of methyl methacrylate, and 180 parts of butyl acrylate,
330 parts of water, 20% aqueous solution of latemul S-180A 20
And a mixed solution of 1.0 part of ammonium persulfate are allowed to flow into the reaction vessel from separate dropping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 4.0. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.02% of the total monomer. The solid content of the obtained emulsion is 4
3.0%, average particle diameter 1080 °.

[0080]

Reference Example 5 With respect to the preparation of a carbonyl group-containing emulsion composition, an emulsion (5) was synthesized. In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 230 parts of water and 20% of latemul S-180A were added.
5 parts of an aqueous solution is charged, and the inside of the reaction vessel is heated to 80 ° C. Next, 5 parts of acrylic acid and 50 ml of diacetone acrylamide
Parts, styrene 220 parts, 2-ethylhexyl acrylate 2
A mixture of 25 parts of a mixture, 400 parts of water, 20 parts of a 20% aqueous solution of latemul S180A, and 1.5 parts of ammonium persulfate are allowed to flow into the reaction vessel from separate dropping tanks over 4 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C.
After the inflow has been completed, the temperature in the reaction
Keep time. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.1. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.15% of the total monomer. The solid content of the obtained emulsion was 43.0%, and the average particle size was 1180 °.

[0081]

Reference Example 6 Regarding the preparation of a polyisocyanate compound,
Synthesis of polyisocyanate compound A was performed. 222 parts of isophorone diisocyanate, 168 parts of hexamethylene diisocyanate, and 2.4 parts of water as a burette agent are dissolved in 130 parts of a 1: 1 (weight ratio) mixed solvent of ethylene glycol methyl ether acetate and trimethyl phosphate, The reaction was performed at a reaction temperature of 160 ° C. for 1.5 hours. The obtained reaction solution was first used under a condition of 1.0 mmHg / 160 ° C. and a
Excess isophorone diisocyanate and hexamethylene diisocyanate and the solvent were distilled off and recovered by a two-stage treatment under the condition of mHg / 200 ° C.

The obtained polyisocyanate compound A is
Cobourette-type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate, the remaining isophorone diisocyanate is 0.7% by weight,
0.1% by weight of remaining hexamethylene diisocyanate, N
The CO content is 19.6% by weight and the viscosity is 20,000 (± 3
000) mPa. s / 40 °, number average molecular weight is about 800
(± 100) and the average number of NCO functional groups was about 3.7. Polyisocyanate compound A is ethyl acetate
A 9.6% solution was obtained.

Next, a polyisocyanate compound B was synthesized. 168 parts of hexamethylene diisocyanate and 1.5 parts of water as a buret agent were mixed with ethylene glycol methyl ether acetate and trimethyl phosphate at a ratio of 1:
1 (weight ratio) in 130 parts of a mixed solvent,
The reaction was performed at 60 ° C. for 1 hour. The obtained reaction solution was subjected to two-stage treatment under a condition of 1.0 mmHg / 160 ° C. in the first time under a condition of 1.0 mmHg / 160 ° C. using a thin-film distillation can. , And the solvent were removed by distillation to obtain a residue.

The residue obtained contained 99.9% by weight of polyisocyanate B (buuret-type polyisocyanate of hexamethylene diisocyanate) and 0.1% by weight of residual hexamethylene diisocyanate. The viscosity of the residue obtained is 1900 (± 200) mP
a. s / 25 °, number average molecular weight is about 600 (± 100)
The average number of NCO functional groups was about 3.3, and the NCO group content was 23.3% by weight.

[0085]

Reference Example 7 Regarding the preparation of a semicarbazide-based curing agent or its terminal-blocked body, a semicarbazide-based curing agent and its terminal-blocked body A1 were synthesized. In a reactor having a reflux condenser, a thermometer and a stirrer, 23 parts of acetone, 23 parts of the polyisocyanate compound A obtained in Reference Example 6 (79.6% ethyl acetate solution, NCO group content 15.6% by weight), Oxyethylene methyl ether (Product name: UNIOX M
1000, manufactured by NOF Corporation, having a hydroxyl value of 56.9), 10 parts, and dibutyltin dilaurate 0.0 as a catalyst.
01 parts were added and reacted at 60 ° C. for 4 hours. Next, 74 parts of hydrazine monohydrate was added to 421 parts of acetone placed in a reactor having a reflux condenser, a thermometer and a stirrer at room temperature over 30 minutes while stirring, and the mixture was further stirred for 1 hour.
The reaction product obtained above was added to this reaction solution with stirring at 40 ° C. over 1 hour, and then further stirred at 40 ° C. for 4 hours. Thereafter, 1183 parts of water was added at 40 ° C. over 30 minutes, and stirring was continued for another 30 minutes. Acetone, ethyl acetate, hydrazine, a reaction product of acetone and hydrazine, water, and the like in the obtained reaction solution were distilled off under reduced pressure by heating to obtain an aqueous dispersion of a semicarbazide-based composition having a solid content of 25%.

FIG. 1 shows the infrared absorption spectrum of this product. 100 parts of cyclohexanone was added to 50 parts (solid content: 10 parts) of an aqueous dispersion of the obtained semicarbazide composition, and the mixture was shaken at 150 rpm for 5 hours, and then 10,000 rpm
and centrifugation at 10 m for 10 minutes. 6.7 parts of a hydrophilic group-containing compound having a polyisocyanate A skeleton in which a polyoxyethylene methyl ether group is introduced as a hydrophilic group is present in the lower aqueous phase, and a polyisocyanate A skeleton is present in the upper cyclohexanone phase. 3.3 parts of the semicarbazide-based curing agent and its terminal blocker were present.

Next, a semicarbazide-based curing agent A2 was synthesized. In a reactor having a reflux condenser, a thermometer and a stirrer, 22 parts of tetrahydrofuran, polyisocyanate A (79.6% ethyl acetate solution, NCO group content of 156) were added.
23% by weight, polyoxyethylene methyl ether (product name: UNIOX M1000, NOF Corporation)
(With a hydroxyl value of 56.9) and 0.001 part of dibutyltin dilaurate as a catalyst, and reacted at 60 ° C. for 4 hours. Next, 7.3 parts of hydrazine monohydrate was added to 147 parts of tetrahydrofuran placed in a reactor having a reflux condenser, a thermometer and a stirrer while stirring at room temperature over 30 minutes, and further stirred for 1 hour. did. The reaction product obtained above was added to this reaction solution with stirring at 10 ° C over 1 hour, and then further stirred at 40 ° C for 4 hours. Thereafter, 182 parts of water were added at 40 ° C. over 30 minutes, and 3 more parts were added.
Stirring was continued for 0 minutes. Tetrahydrofuran, ethyl acetate, hydrazine, water and the like in the obtained reaction solution were distilled off under reduced pressure by heating to obtain an aqueous dispersion of a semicarbazide-based curing agent having a solid content of 30%.

FIG. 2 shows the infrared absorption spectrum of this product. Further, a semicarbazide-based curing agent B was synthesized. After 80 parts of hydrazine monohydrate was added to 1000 parts of isopropyl alcohol in a reactor having a reflux condenser, a thermometer and a stirrer with stirring over about 30 minutes at room temperature, polyisocyanate B (NCO group content 23%) was added. .3
(% By weight) in 576 parts of tetrahydrofuran was added at 10 ° C. over about 1 hour.
Stirring was continued at 0 ° C. for 3 hours and 1000 parts of water were added. Subsequently, isopropyl alcohol, hydrazine, tetrahydrofuran, water and the like in the obtained reaction solution were distilled off under reduced pressure by heating to obtain 168 parts of a semicarbazide derivative having a biuret structure. FIG. 3 shows the infrared absorption spectrum of this product.

[0089]

Example 1 Emulsion (1) 2 synthesized in Reference Example 1
After mixing 5 parts with 75 parts of the emulsion (2) synthesized in Reference Example 1, an aqueous dispersion 10 having a solid content concentration of 30% of the semicarbazide-based curing agent obtained in Reference Example 7 and its terminal blocker (A1) was prepared. After adding 0.5 parts and mixing at room temperature for 30 minutes, a mixture was prepared according to Formulation A or Formulation B, and then subjected to each test. Table 1 shows the results.

[0090]

Example 2 Emulsion (1) 2 synthesized in Reference Example 1
After mixing 5 parts with 75 parts of the emulsion (2) synthesized in Reference Example 1, 10.5 parts of an aqueous dispersion having a solid concentration of 25% of the semicarbazide-based curing agent (A2) obtained in Reference Example 7 was added. After mixing at room temperature for 30 minutes, the mixture was prepared according to Formulation A or Formulation B, and then subjected to each test. Table 1 shows the results.
Shown in

[0091]

Example 3 Emulsion (1) 2 synthesized in Reference Example 1
After mixing 5 parts with 75 parts of the emulsion (2) synthesized in Reference Example 1, 5.3 parts of a 25% solids aqueous dispersion of the semicarbazide-based curing agent (B) obtained in Reference Example 7 was added. Then, the mixture was mixed at room temperature for 30 minutes to prepare a blend according to Formula A or Formula B, and then subjected to each test. Table 1 shows the results.

[0092]

Comparative Example 1 Emulsion (1) 2 synthesized in Reference Example 1
After mixing 5 parts with 75 parts of the emulsion (2) synthesized in Reference Example 1, a 5% aqueous solution of adipic dihydrazide 1 was added.
After adding 24 parts and mixing at room temperature for 30 minutes, a mixture was prepared according to Formulation A or Formulation B, and then subjected to each test. Table 1 shows the results.

[0093]

Comparative Example 2 Emulsion (2) 1 synthesized in Reference Example 2
In 00 parts, the semicarbazide-based curing agent (B) obtained in Reference Example 7
5.7 parts of an aqueous dispersion having a solid concentration of 25% was added and mixed at room temperature for 30 minutes to prepare a blend according to Formula A or Formula B, and then subjected to each test. Table 1 shows the results.

[0094]

Example 4 Emulsion (3) 1 synthesized in Reference Example 3
5.7 parts of an aqueous dispersion having a solid concentration of 25% of the semicarbazide-based curing agent (B) obtained in Reference Example 7 was added to the mixture, and the mixture was mixed at room temperature for 30 minutes. After that, it was subjected to each test. Table 1 shows the results.

[0095]

Example 5 Emulsion (4) 1 synthesized in Reference Example 4
5.7 parts of an aqueous dispersion having a solid concentration of 25% of the semicarbazide-based curing agent (B) obtained in Reference Example 7 was added to the mixture, and the mixture was mixed at room temperature for 30 minutes. After that, it was subjected to each test. Table 1 shows the results.

[0096]

Example 6 Emulsion (5) 9 synthesized in Reference Example 5
After mixing 0 parts and 10 parts of the emulsion (1) synthesized in Reference Example 1, 18 parts of an aqueous dispersion having a solid concentration of 25% of the semicarbazide-based curing agent (B) obtained in Reference Example 7 was added,
After mixing at room temperature for 30 minutes to form a blend according to Formula A or Formula B, the mixture was subjected to each test. Table 2 shows the results.

[0097]

Comparative Example 3 Emulsion (5) 1 synthesized in Reference Example 5
In 00 parts, the semicarbazide-based curing agent (B) obtained in Reference Example 7
Was added and mixed at room temperature for 30 minutes to prepare a blend according to Formula A or Formula B, and then subjected to each test. Table 2 shows the results.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

The crosslinked aqueous emulsion composition of the present invention can be stored and used as a single solution, and its film has a high crosslink density, is tough, and has heat resistance, chemical resistance, water resistance, weather resistance, adhesion, and initial gloss. Excellent in gloss retention and the like, and can be obtained at a relatively low temperature. Therefore, it is useful for various uses such as paints, underlaying materials or finishing materials for building materials, adhesives, pressure-sensitive adhesives, paper processing agents, and finishing agents for woven fabrics.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of one example of the compound of the present invention.

FIG. 2 is an infrared absorption spectrum of another example of the compound of the present invention.

FIG. 3 is an infrared absorption spectrum of another example of the compound of the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 15/347 D06M 15/347 15/564 15/564 D21H 17/46 D21H 3/48

Claims (6)

[Claims] 1. A crosslinked aqueous emulsion composition comprising a polycarbonyl compound and a polyfunctional semicarbazide-based curing agent and / or a terminal blocker [A] thereof, wherein at least one polycarbonyl compound is present in the molecule. The acid value obtained by polymerizing a monomer mixture containing 0.5% by weight or more of an ethylenically unsaturated monomer having an ald group or a keto group and a carboxylic acid group-containing unsaturated monomer is 25 mg KOH / g or more. A crosslinked aqueous emulsion composition comprising the carbonyl group-containing copolymer [B]. 2. The polyfunctional semicarbazide-based curing agent is derived from a polyisocyanate compound.
2. The crosslinked aqueous emulsion composition according to item 1. 3. The crosslinked aqueous emulsion composition according to claim 2, wherein the polyfunctional semicarbazide-based curing agent is represented by the following formula (1). Embedded image (Wherein R ¹ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a carbon number A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkylene group having 1 to 6 carbon atoms not substituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; From the group consisting of arylene diisocyanates of numbers 6 to 20, and aralkylenediisocyanates of 8 to 20 carbon atoms which are unsubstituted or substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Polyimide having no terminal isocyanate group, derived from at least one selected from trimer to 20-mer oligomer of diisocyanate Cyanate residues or R,
¹ represents a triisocyanate residue having no terminal isocyanate group, which is derived from an alkylene diisocyanate having 2 to 20 carbon atoms and substituted by an isocyanatoalkyl group having 1 to 8 carbon atoms. R ² is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 to carbon atoms. Represents an arylene group having 6 to 10 carbon atoms and substituted by an alkoxy group of 8; Each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n is 0 or 1. l
And m are each independently 0 or a positive integer, provided that 3 ≦ (l + m) ≦ 20. ) 4. A polycarbonyl compound comprising a carbonyl group-containing copolymer [B] and a polycarbonyl polymer composition [C].
Wherein the polycarbonyl polymer composition [C] contains 0.5% by weight or more of an ethylenically unsaturated monomer having at least one ald group or keto group in a molecule, and other polyunsaturated monomer. The crosslinked aqueous emulsion composition according to claim 1, which is an aqueous emulsion composition obtained by polymerizing a monomer mixture containing a saturated monomer and having an acid value of less than 25 mgKOH / g. 5. The method according to claim 5, wherein the polycarbonyl compound is a polycarbonyl polymer composition [C] and a monomer mixture.
The crosslinked aqueous emulsion composition according to claim 4, which is an aqueous emulsion composition [D] obtained by polymerizing a carbonyl group-containing copolymer [B]. 6. A polycarbonyl compound, wherein a carbonyl group-containing copolymer [B] at least partially solubilized with an alkali in an aqueous medium and a monomer mixture,
The crosslinked aqueous emulsion composition according to claim 4, which is an aqueous emulsion composition [E] obtained by polymerizing the polycarbonyl polymer composition [C].